Quaternary nitrogen compounds



Patented Sept. 16, 1941 UNITED STATES PATENT OFFICE QUATERNARY NITROGEN COMPOUNDS Gerhard Balle, Frankfort-on-the-Main, and Karl Hors Hofheim in Tannus, Germany, assignors, by mesne assignments, to General Aniline &

Film Corporation, New York, N. Y.., a corporation of Delaware No Drawing. Application March. 3, 1939, Serial No. 259,632. In Germany October 10, 1935 6 Claims. (Cl. 260-561) The present invention relates to quaternary nitrogen compounds.

In U. S. application Serial No. 104,334, filed October 6, 1938, of which this application is a continuation-in-part, quaternary ammonium compounds are described which are obtainable by causing halogen carboxylic acids or a salt or an ester thereof to react with a disubstituted aminoacyiamide.

We have found that quaternary nitrogen compounds in which several carboxylic groups or their functional derivatives are united through carbon links with the quaternary nitrogen atom, are manufactured by causing a halogencarboxylic acid amide to act upon a disubstituted amimary or secondary amine of the aliphatic, cycloaliphatic or aromatic series. In this way the ester group of the quaternary ammonium comnoacylamide obtainable, for instance, by reaction of halogenacylamides with secondary amines according to the scheme.

R1\ /R4 NH-l-halogen R=.CO.N Ra Rs RI N.R:.C0.N/ +H halogen R1 R5 1 wherein R3 stands for an aliphatic hydrocarbon amide mixture from chloracetic acid and the,

primary amines obtainable from palmnut oil fatty acid, chloracetic acid methylstearylamide, alpha-chloropropionic acid oleyl-amide, alphabromo-stearic acid amide and others. The reaction with the secondary amines proceeds in some cases without external heat supply, and so rapradical, R1 and R2 stand for lower aliphatic hydrocarbon radicals which may be substituted and R4 and R5 stand for hydrogen or a hydrocarbon radical which may be substituted.

The formation of the quaternary nitrogen compounds according to the present invention corresponds to the following scheme:

Ri\ /R4 /N.R:.CO.N halogen.Rc.X R: R5

halogen /Ri /I]I.R;.C0.N R: Bax RI wherein R1, R2, R3, R4 and R5 have the abovementioned signification, R6 represents an aliphatic hydrocarbon radical and X stands for amidated COOH.

The two components may be caused to react in the presence or absence of a suitable solvent or diluent, for example, in water or in an organic solvent, generally at a temperature of 30 C.-120 0. Depending on the nature of the parent materials, the reaction takes place already when mixing the reaction agents or heating under pressure may be necessary.

The amidated quaternary compounds may be further obtained by causing a halogencarboxylic acid ester to react with a vdisubstituted amino acylamide and by causing the quaternary ammonium compound thus formed which contains esterified COOH to react with ammonia or a priidly that the heat evolved must be led away, and in other cases the components must be heated together, under pressure it necessary. The reaction may also be carried out in the presence 01 solvents. The application of an agent for binding hydrogen halide is useful, if the second-1 ary base is not used in excess.

Halogen carboxylic acid amides suitable for the reaction with the afore-mentioned aminoacylamides are, for example:

- l Furthermore. the condensation may first be carried out with aliphatic halogen-carboxylic acid esters, for instance:

C1.OH2.COOCH1 Bl'.CHz-CH1.COOC1H.

oi.on.oooom "Hu- 7 and when the reaction is complete the esterifled suitable for or aralkyl; the amide radical may also contain any other substituents. Furthermore, there may be used anyhalogen-carboxylic acid which con- 7 tains a reactive halogen atom.

The quaternary nitrogen compounds obtainable by the present invention are in the pure state colorless, in part crystallizable, in part oily to fattyor wax-like bodies which in general are soluble in water or, especially those of high molecular weight, disperse in water so as to form an emulsion. Uses of these compounds are as softeners for textiles and as agents for the improvement of the fastness qualities of substantive dyeings.

The new nitrogen compounds are, for instance,

suitable for use in the textile industry.

The following examples serve to illustrate the invention, but they are not intended to limit thereto; the parts are by weight:

1. 168 parts of dimethylamino-acetostearylamide are melted together with 130 parts of chloracetododecylamide for 4 hours at 90 C. to 120 C., while stirring, until a sample of the product is soluble in warm water or disperses therein so as to torm an emulsion. The yield of N-dimethyl-N- acetostearylamide betaine dodecylamide chloride of the formula:

is quantitative. The anhydrous product has a wax-like structure.

The dimethylamino-acetostearylamide is obtained by treating in a pressure vessel for 3 hours at a temperature of 80 C. to 100 C. 328 parts of chloracetostearylamide with 220 parts of a solution of dimethylamine of 45 per cent. strength. After distillation of the solvent, the dimethyl- ,amine hydrochloride formed as by-product is extracted by means of hot water (with addition of sodium chloride) at 85 C. The separated oilsolidifles after cooling and is pure dimethylaminoacetostearylamide. The yield almost corresponds with that foretold by theory.

2. 102 parts of dimethylamidoacetamide and 360 parts of chloracetomethylstearylamide in 500 parts of benzene are boiled for-about 5 to 7 hours in a reflux-apparatus. On cooling the reaction product precipitates from the benzene solution from which it may be separated by filtering or pouring oif. The residual solvent may be eliminated by heating under reduced, pressure. The remaining fat-like mass dissolves in water to a a clear solution.

3. 298 parts of dibutylaminoacetodibutylamide are mixed with 205 parts of chloracetodibutylamide; the addition occurs thereby with evolution of heat, care being taken that the temperature does not rise above about 80 C. to 100 C.

The product obtained is soluble in neutral, acid and alkaline solutions.

- C. together with 260 parts of chloroacetic acid I I come soluble in water.

4. 188 parts of beta-diethylamino-propionic acid-hydroxy-ethylamide and 108 parts of chloroacetic acid methylester are heatedto about 70 to 0., reaction occurring thereby. In case the temperature rises rapidly the vessel must be cooled from outside so that the temperature does not exceed about 100 C. to 120 C.

The ester chloride obtained having the formula:

CzHI Cl N.cm.crn.connomomon 0,11. vmootcn'z is mixed with a solution of 2'70 parts of oleylamine in 500 parts of benzene and then heated for several hours on the water bath in a reflux apparatus. After the benzene as well as the methanol formed during the reaction have been distilled, a colorless watersoluble product is obtained.

5. 178 parts of dimethylamino-acetanilide and 275 parts of beta-chloropropionic acid dodecylamide are heated together to about 80 C. to 100 C., while stirring, until the product has bemass is obtained, whose solutions in water have a strong foaming action.

6. 212 parts of dimethylamino-acetoethylcyclohexylamide and 180 parts of chloroacetic acid di-.

ethanolamide are heated together, while stirring, to about 80 C. to 100 C.,.until the reaction product has become soluble in water. a

7. 158 parts of dipropyl aminoacetamlde or heated together with 180 parts of chloroacetobenzyl amide to about 70 C. to C. until the mass has become watersoluble.

Instead of chloroacetobenzylamide there may be used 161 parts of. chloroacetopiperidide: a watersoluble product is likewise obtained thereby.

8. 158 parts of alpha-dimethylaminobutyric acid dimethylamide are melted at 90 C. to

dodecylamide, until the mass has become soluble in water. A fat-like, almost colorless product is obtained.

9. 102 parts of dimethylaininoacetamide are melted at 100 C. to C. together with 315 parts of alpha-chloro-stearic acid amide, until the reaction mixture has become watersoluble. The product thus obtained is an almost colorless fat-like mass.

We claim! 1. The products of the general formula:

R1 lialogen Ra \a-ai-o'o -r/ wherein R1 and R2 represent lower aliphatic hydrocarbon radicals, R4 and R5 represent members-of the groupconsisting of hydrogen, hydrocarbon radicals and aliphatic hydrocarbon rad icals substituted by hydroxy-groups, R3 and Re represent aliphatic hydrocarbon radicals, and x means 'amidated CODE.

2. The products of the general formula:

wherein R1 and R2 represent lower aliphatic hydrocarbon radicals, R: and Re represent allphatic hydrocarbon radicals, R4 is a member of A feebly colored fat-like the group consisting of hydrogen, hydrocarbon 5. The product of the Iormula: radicals and aliphatic hydrocarbon radicalssubcan stituted by hydroxy groups, R5 represents an aliphatic hydrocarbon radical of at least 8 carbon &' atoms and X means amidated COOH. 5 ali: H: H 3. The products 0! the general formula:

BI 01 H c n- 6. The product of the formula: R: H: R: 10 0B. Oi H l -cmcowherein R1 and R: represent lower aliphati hydrocarbon radicals, R5 represents an aliphatic H hydrocarbon radical of at least 8 carbon atoms and X means amidated COOH. 15 0-NH-CnHu 4. The product 01 the formula: GERHARD 3mm KARL HORST.

cH,-co-N CH; H: H CuHu 

